The invention relates to the use of an emulsion polymer in aqueous cosmetic compositions, wherein the emulsion polymer is obtainable by emulsion polymerization of a monomer mixture A comprising from 50 to 100% by weight, based on the monomer mixture, of C1-C18 alkyl (meth)acrylates, vinyl esters, vinylaromatic compounds or mixtures thereof in the presence of a Polymer B which has been built up from
b1) from 5 to 50% by weight of monomers having at least one ionic group or one group which can be converted into an ionic group,
b2) from 0 to 95% by weight of C1-C18 alkyl (meth)acrylates, vinyl esters, vinylaromatic compounds or mixtures thereof, and
b3) from 0 to 50% by weight of further monomers,
the glass transition temperature of the polymer built up from monomer mixture A being less than or equal to that of the polymer B.
Aqueous cosmetic compositions, including nail varnish compositions, are already known from EP-A-424 122. As binders, the compositions described therein comprise an emulsion polymer with a core/shell structure, where the glass transition temperature of the (hydrophilic) shell is at least 10xc2x0 C. lower than that of the core. The nail varnish compositions described show a still inadequate adhesion to keratin-containing substrates, in other words to fingernails.
EP-A-727 441 (O.Z. 0050/45626) discloses emulsion polymers which are obtainable by polymerization in the presence of a polymeric protective colloid.
It is an object of the present invention to provide aqueous cosmetic compositions which have good adhesion to keratin-containing substrates and produce films with good water resistance, good gloss, sufficient hardness and high transparency.
We have found that this object is achieved by the use defined at the outset.
As used below, the term monomer represents free-radically copolymerizable compounds having at least one ethylenically unsaturated group.
The emulsion polymer is preferably prepared by emulsion polymerization of the monomer mixture A) in the presence of a polymer B).
The polymer B) consists preferably of
from 10 to 30% by weight of monomers b1),
from 60 to 90% by weight of monomers b2) and
from 0 to 30% by weight of monomers b3).
The percentages by weight are based in each case on the polymer B).
Suitable monomers b1) can be acidic or anionic, basic or cationic, or amphoteric monomers.
It is also possible for anionic and cationic monomers to be present simultaneously in polymer B), with one of the two types of monomer being in excess, from a molar standpoint, so that the dispersion prepared therewith is anionic or cationic. This can be sensible, for example, when one of the two types of monomer brings about an additional advantage, such as improved adhesion or dispersion stability.
Examples of anionic or acidic monomers are polymerizable carboxylic acid derivatives, such as: (meth)acrylic acid, maleic acid and its anhydrides and monoesters, fumaric acid and its monoesters, itaconic acid;
unsaturated sulfonic acid derivatives, such as: styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid or salts thereof;
unsaturated phosphoric or phosphonic acid derivatives, such as: vinylphosphonic acid or the monophosphates of polymerizable alcohols such as butanediol monoacrylate or hydroxyethyl methacrylate.
Examples of cationic or basic monomers are (meth)acrylic esters or (meth)acrylamides of amino alcohols, such as dialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl(meth)acrylamides, for instance N,N-dimethylaminoethyl (meth)acrylates, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminopropylacrylamide, dialkylaminostyrenes, for example N,N-dimethylaminostyrene and N,N-dimethylaminomethylstyrene, vinylpyridines, such as 4-vinylpyridine and 2-vinylpyridine, and also compounds which can be prepared by quaternization of the abovementioned basic monomers using known quaternizing reagents such as alkyl halides, benzyl halides, dialkyl sulfates, etc.
Examples of amphoteric monomers are N-(3-sulfopropyl)-N-methacryloyloxyethyl-N,N-dimethylammonium betaine and N-carboxymethyl-N-methacryloyloxyethyl-N,N-dimethylammonium betaine.
Acid groups or tertiary amino groups can be converted into ionic groups by forming salts or by quaternization.
Examples of monomers b2) (principal monomers) are C1-C9-alkyl, especially C1-C8-alkyl (meth)acrylates, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and n-butyl methacrylate.
Lauryl or stearyl (meth)acrylates can also be mentioned.
Also suitable in particular are mixtures of alkyl (meth) acrylates.
Vinyl esters of carboxylic acids having 1 to 20 C atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
Suitable vinylaromatic compounds are vinyltoluene, xcex1- and p-methylstyrene, xcex1-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and, preferably, styrene.
The monomers b2) are also preferably employed in a mixture.
Vinylaromatic compounds such as styrene are frequently employed, for example, in a mixture with C1-C18-alkyl (meth)acrylates, especially with C1-C18-alkyl (meth)acrylates.
Examples of further ethylenically unsaturated monomers b3) are hydroxyl-containing monomers such as hydroxyalkyl (meth)acrylates, for example hydroxypropyl or hydroxyethyl (meth)acrylate, amides or substituted amides of ethylenically unsaturated mono- or dicarboxylic acids, for example acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and the N-methylolacrylamides and N-methylolmethacrylamides which are etherified with C1-C6 monohydric alcohols. Crosslinking monomers, for example with two vinyl groups, although they can also be used, are preferably absent from the polymer B or, if present, then only in small amounts, for example below 0.2% by weight, based on the polymer B.
Also deserving of mention are nitrites, vinyl halides and nonaromatic hydrocarbons.
Examples of nitrites are acrylonitrile and methacrylonitrile.
The vinyl halides are ethylenically unsaturated compounds substituted by chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride.
Nonaromatic hydrocarbons having 2 to 8 C atoms and one or two olefinic double bonds which may be mentioned are butadiene, isoprene and chloroprene, and also ethylene, propylene and isobutylene. Nonaromatic hydrocarbons having two double bonds are less preferred principal monomers for preparing the protective colloid.
The weight-average molecular weight (Mw) of the polymer B) is preferably more than 10,000, particularly preferably more than 20,000 to 200,000 and, with very particular preference, from 40,000 to 120,000 (determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).
The polymer B) can be prepared, for example, by bulk polymerization, in other words without solvent, orxe2x80x94preferablyxe2x80x94by solution polymerization.
The polymers B) prepared by bulk or solution polymerization are preferred, since the polymers are more uniform in structure and include an incorporated hydrophobic (oil-soluble) initiator.
Examples of suitable solvents are those having a boiling point of below 100xc2x0 C. at 1 bar or those which with water form an azeotrope which can easily be distilled off from the aqueous polymer dispersion if desired. Advantageously, it is also possible to use film-forming aids, such as butylglycol, butyldiglycol or butoxypropanol, as solvents. In this way, subsequent addition of these auxiliaries becomes unnecessary.
Examples which may be given of solvents are butanol, isobutanol, propanol, ethanol, methanol and methyl ethyl ketone.
The ethylenically unsaturated monomers can be polymerized, for example, in a known manner by means of anionic or preferably free-radical polymerization, preferably in the presence of initiators. Examples of free-radical initiators are azobiscarboxamides, azobiscarbonitriles, peracid esters or peroxides. The amount of initiator is preferably from 0.2 to 5, particularly preferably from 0.5 to 3% by weight, based on the monomers. The polymerization temperature is preferably from 50 to 150xc2x0 C., particularly preferably from 80 to 130xc2x0 C. It is also possible if desired to add regulators, examples being mercaptoethanol, tert-dodecyl mercaptan or diisopropylxanthogen sulfide, preferably in amounts of from 0 to 3% by weight, based on the monomers.
The polymer B) can be prepared, for example, in one or more stages. In particular it is possible, for example, first to prepare a polymer having a high acid content and then, in the presence of said polymer, to prepare a polymer having a lower acid content (or acid number=0), as is described, for example, in EP-A 320 865.
In the case of the present invention, however, a multistage preparation of this kind is not necessary, and so the single-stage preparation is preferred. For the polymerization the monomers can be introduced as an initial charge or else (preferably) can be metered in continuously.
The polymer B) is obtained as a dispersion or, preferably, solution in the organic solvent. The solids content is preferably from 50 to 95, especially from 60 to 85% by weight.
The polymer B) is then used as a protective colloid in the emulsion polymerization.
For this purpose the polymer B) can be introduced as an initial charge in water and/or can be added to the water in the course of emulsion polymerization together with the monomers to be polymerized.
The polymer B) can be used in the form of its organic solution, for example in the case of solution polymerization, or else in solvent-free form, for example in the case of bulk polymerization. Alternatively, it is possible first to convert it into an aqueous dispersion or solution, and if desired to remove solvent by distillation.
Before or during conversion to the aqueous phase, some or all of the acid groups or anhydride groups of the polymeric protective colloid are converted into salt groups; in other words they are neutralized.
Suitable neutralizing agents are, firstly, mineral bases such as sodium carbonate or potassium carbonate and also ammonia, and secondly organic bases, for example amino alcohols, especially 2-amino-2-methyl-l-propanol (AMP), triethanolamine, triisopropanolamine (TIPA), monoethanolamine, diethanolamine, tri[(2-hydroxy)-1-propyl]amine, 2-amino-2-methyl-1,3-propanediol (AMPD) or 2-amino-2-hydroxymethyl-1,3-propanediol, and also diamines such as lysine.
Insofar as the polymer B) is not already present in an aqueous phase and, accordingly, the conversion to salt groups has already taken place, conversion to salt groups is carried out before or during the addition of the polymer B) to the polymerization batch of the emulsion polymerization.
The proportion by weight of the polymer B) is preferably from 2 to 40 parts by weight, particularly preferably from 5 to 25 parts by weight, based on 100 parts by weight of the polymer obtained by emulsion polymerization (in other words the sum of polymer B and monomer mixture A).
In the emulsion polymerization, no further emulsifiers, protective colloids or other dispersing auxiliaries are required, and therefore are preferably not employed.
The monomers of the monomer mixture A) that are to be polymerized essentially comprise the monomers b1) to b3) already mentioned above, with suitable monomers b2 also including aliphatic hydrocarbons having 2 to 8 C atoms and two double bonds, and suitable monomers b3) also including crosslinking monomers, such as butanediol acrylate and divinylbenzene.
The monomer mixture A) consists preferably to the extent of from 0 to 100, particularly preferably to the extent of from 40 to 100% by weight, of the monomers b2) (principal monomers).
Monomers b1) can but need not necessarily be used; if they are, their proportion, however, is generally in each case below 10% by weight, preferably below 5% by weight, and, with particular preference, below 3% by weight.
Further monomers b3) can likewise be used, for example in amounts of from 0 to 100% by weight, preferably from 0 to 60% by weight. The weight data are based on the resulting polymer.
The glass transition temperature (Tg) of the monomer mixture A (that is, of a polymer which has been built up from the monomer mixture A) is less than or, at the most, equal to the glass transition temperature of the polymer B.
The Tg of the monomer mixture A is with particular preference at least 10xc2x0 C., especially 20xc2x0 C., lower than that of the polymer B.
The Tg of the monomer mixture A is preferably from 0 to 100xc2x0 C. and with particular preference from 5 to 50xc2x0 C.
The Tg of the polymer B is preferably from 10 to 150xc2x0 C. and with particular preference from 40 to 130xc2x0 C.
In this context, the Tg is calculated in accordance with Fox from the Tg of the homopolymers formed from the monomers (T.G. Fox, Bull. Am. Phys. Soc. Ser II, 1 (1956)123)       1          T      g        =                    X        A                              T          g                ⁡                  (          A          )                      +                                       X                ⁢        B                              T          g                ⁡                  (          B          )                      +    …  
Tg(A),(B): Tg of the homopolymer of monomer (A), (B)
XA, XB: mass fraction of the monomer (A), (B)
The emulsion polymerization can be carried out in a customary manner, for example at from 30 to 95xc2x0 C. in the presence of a water-soluble initiator.
Examples of suitable initiators are sodium, potassium and ammonium persulfate, tert-butyl hydroperoxides, water-soluble azo compounds, or redox initiators.
In the case of hydrogen peroxide as initiator it is preferred also to use small amounts of Cu(II) or Fe(III) as catalyst.
The aqueous emulsion polymer dispersion obtained after the emulsion polymerization preferably has a solids content of from 10 to 65, preferably from 30 to 60 and, with particular preference, from 40 to 55% by weight.
The emulsion polymer, or the aqueous dispersion, is used as a binder for aqueous cosmetic compositions, especially for aqueous nail varnish compositions.
The novel aqueous cosmetic compositions can comprise further constituents, examples being pigments, dyes, dispersants, wetting agents, thickeners, humectants, leveling agents, preservatives, foam inhibitors, gelling agents, buffers and UV absorbers. The selection of such possible constituents is within the ability of the skilled worker in the cosmetics field.
Any pigments or dyes used should be relatively lightfast and non-bleeding. Substances which impart a pearl luster, such as mica, guanine, bismuth oxychloride or titanium dioxide on mica, can likewise be used. Numerous examples of suitable pigments and dyes are given in Madison G. deNavarre, The Chemistry and Manufacture of Cosmetics, Vol. 4, pp.996-998 (2nd ed.).
Dispersants and wetting agents are frequently used as surface-active agents in these nail coating formulations in order to assist the uniform distribution of the pigment. Inorganic pigments are inherently hydrophilic and can readily be dispersed in an aqueous emulsion system. Organic pigments are hydrophobic and necessitate a dispersant or wetting agent, which reduces the surface tension and allows uniform distribution. A listing of suitable surface-active agents is given in Encyclopedia of Chemical Technology, Surfactants, Vol. 19, p. 584 (1969), and the choice to be made in each case is within the knowledge and ability of the skilled worker.
Thickeners serve to prevent separation and settling. Examples of suitable thickeners are natural gums, such as guar, gum arabic, cellulose and cellulose derivatives, silicates, such as V-gum(copyright), clays, such as stearalkonium hectorite, and synthetic polymers, such as acrylates, for example Carbopol(copyright) and Acrysols(copyright).
Examples of humectants are mono- and polyglycols, mono- and polyglycerols, sugar alcohols, alkylene oxides and polyalkylene oxides, especially ethylene and propylene oxides (EO and PO), saccharides, glucosides, amino acids, urea and adducts of EO and/or PO with these compounds. The humectants transmit moisture to the skin and are generally used in amounts of from 0.01 to 30% by weight, preferably from 0.1 to 10% by weight, based on the cosmetic composition.
Leveling agents can be added to reduce the temperature at which the film is able to form. The leveling agents therefore function only during film formation. For the purposes of the invention, these agents must be soluble in water. One group of appropriate leveling agents comprises the glycol ethers, such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether.
To prevent bacterial and fungal growth during storage of the nail coating formulations it is common to use preservatives. Preservatives suitable for this purpose are those generally used, for example lower alkyl esters of p-hydroxybenzoic acid, such as methyl, ethyl, butyl and hexyl p-hydroxybenzoate, organic salts, such as potassium sorbate, inorganic salts, such as mercury salts, and formaldehyde and formaldehyde donors.
To prevent foaming and the formation of bubbles during preparation and application to the nails it is possible to use foam inhibitors. Examples of suitable foam inhibitors are unsubstituted and substituted organopolysiloxanes, such as methylsilicone and diethylsilicone, silicon dioxide, mixtures of silicon and silicon dioxide, and of organopolysiloxanes and silicon dioxide, and polyoxyethylene-polyoxypropylene condensates.
Gelling agents remove heavy metal ions, which may impair the stability of nail varnishes. Suitable gelling agents are ethylenediaminetetraacetic acid (EDTA) and its mono- and tetrasodium salt, and tetrasodium pyrophosphate.
If necessary, the nail coating formulation is buffered so that the pH is preferably from 7 to 10, more preferably 8.0xc2x10.5.
The purpose of UV absorbers is to prevent the damaging effects of UV rays on the polymer, chalking of the pigment or dye, and embrittlement of the nail coating film. A listing of suitable UV absorbers is given in Encyclopedia of Chemical Technology, Vol. 21, pp.115-122 (1969).
The content of the emulsion polymer in the cosmetic composition is preferably 1-70% by weight, more preferably 20-65% by weight and, with particular preference, 25-50% by weight, based on the overall weight of the cosmetic composition. If the amount used is less than 1%, the effect according to the invention may not be obtained. If, on the other hand, it is greater than 70% the viscosity of the novel composition is too high.
The dispersion of the emulsion polymer contains little coagulum and features fine disperse particles.
The aqueous cosmetic compositions, especially nail varnish compositions, have a high water stability, in other words low water absorption, good film-forming properties, good gloss and, in particular, good adhesion to keratin-containing substrates such as fingernails.